JPH0561143A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver image ultrahigh in contrast even with a developing solution of low pH by incorporating a specified hydrazine compound and an anionic surfactant. CONSTITUTION:The photosensitive material contains the specified hydrazine compound represented by formula I and the anionic surfactant. In formula I, R1 is an aliphatic or aromatic ground partially substituted by -O-(CH2CH2O)n or the like or a quaternary ammonium ion; n is an integer of >=3; G1 is -CO-, -COCO-, -P(O)(G2R2)-, or the like; G2 is a simple bond or -O- or the like; R2 is an aliphatic or aromatic group or H; one of A1 and A2 is H and the other is H, acyl, alkyl, or arylsulfonyl, thus permitting the hydrophobic hydrazine compound to be stably dispersed and ultrahigh contrast negative images to be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and in particular, it contains a hydrophobic hydrazine compound in a stable dispersion and forms a superhigh contrast negative image using a stable developing solution having a low pH. The present invention relates to a silver halide photographic light-sensitive material that can be used.

[0002]

The presence of hydrazine compounds in silver halide emulsion layers for various purposes is described, for example, by Mees, "The
Theory of the Photographic Proess "Third Edition, (19
66) 281, Research Disclosure, 23
510 (1983), U.S. Pat.
243739, 4272614, 432364
No. 3, No. 4385108, No. 4268969, etc. That is, the hydrazine compound may be used in combination with an internal latent image type silver halide to form a direct positive image, or separately, it may be used in combination with a surface latent image type silver halide to obtain high sensitivity. Can also be used to form super-high contrast negative images.

However, in the method using this hydrazine compound, since the pH of the developing solution is set to be very high, p
There is a problem that the H value tends to fluctuate, and variations in the pH value tend to cause variations in the results of photographic characteristics. U.S. Pat. Nos. 4,988,604 and 4,994,365
In order to solve the above-mentioned problems, JP-A No. 1993-237 discloses that the activity of the hydrazine compound is increased so that the effect of sensitizing and increasing the contrast of the hydrazine compound can be exhibited in a developing solution having a lower pH.

When a hydrazine compound is used in a silver halide light-sensitive material, the hydrazine compound should not be eluted in the developing solution to cause contamination of the solution or adversely affect the silver halide in the emulsion layer in the vicinity. It is desirable to use a diffusion-resistant or water-insoluble hydrazine compound. However, it is not easy to stably disperse such a water-insolubilized hydrophobic hydrazine compound in a hydrophilic silver halide emulsion.

Conventionally, as a method of dispersing a hydrophobic photographic additive in a silver halide emulsion, a method of dissolving it in a water-miscible organic solvent such as methanol and adding it to the emulsion is known. However, due to its low solubility in water,
When added, precipitation occurs or the dispersibility during coating deteriorates,
Furthermore, there is a problem that the film quality is deteriorated or the reactivity of the hydrazine compound is lowered. US Patent No. 4,
Nos. 988,604 and 4,994,365 do not solve this problem because a large amount of a hydrophobic hydrazine compound is added to a silver halide emulsion.

[0006]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material containing a hydrophobic hydrazine compound stably dispersed therein so that the intended purpose thereof can be sufficiently fulfilled.

[0007]

The object of the present invention has been achieved by a silver halide photographic light-sensitive material containing a hydrazine compound represented by the following general formula (1) and an anionic surfactant. ..

[0008]

[Chemical 4]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and -O- (CH ₂ CH ₂ O) _n- as a part of the substituent.
, -O- (CH ₂ CH (CH ₃ ) O) _n -or -O- (CH ₂ CH (OH) CH ₂ O) _n-
(Where n is an integer of 3 or more), or a group containing a quaternary ammonium cation as a part of the substituent. G ₁ is -CO- group, -COCO- group, -C
S-group, -C (= NG ₂ R ₂ )-group, -SO- group, -SO ₂ -group or -P (O)
Represents a (G ₂ R ₂ )-group. G ₂ is a mere bond, -O- group, -S-
Group or -N (R ₂ )-group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. good. A
_{One of 1} and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or arylsulfonyl group.

The general formula (1) will be described in more detail. In the general formula (1), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly 1 carbon atom
To 20 straight, branched or cyclic alkyl groups. This alkyl group has a substituent. In the general formula (1), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ is substituted.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. Chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 carbon atoms)
~ 30), an alkoxy group (preferably having a carbon number of 1 to 1)
30), substituted amino group (preferably having 1 to 3 carbon atoms)
Amino group substituted with 0 alkyl group), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having carbon number) 1 to 40), a phosphoric acid amide group (preferably having 1 to 40 carbon atoms), and the like.

The aliphatic group, aromatic group or their substituents for R ₁ is -O- (CH ₂ CH ₂ O) _n- , -O (CH ₂ CH (CH ₃ ) O) _n- , or -O. _{- (CH 2 CH (OH)} CH 2 O) n - or contains a, or it contains a quaternary ammonium cation. n is an integer of 3 or more, preferably an integer of 3 or more and 15 or less. R
₁ is preferably the following general formula (2), general (3), general (4)
Alternatively, it is represented by the general formula (5).

[0013]

[Chemical 5]

In the formula, L ₁ and L ₂ are -CONR ₇ -groups, -NR ₇ CONR
_{It represents an 8} -group, a -SO ₂ NR ₇ -group or a -NR ₇ SO ₂ NR ₈ -group, which may be the same or different. R ₇ and R
₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable.
m is 0 or 1. R ₃ , R ₄ and R ₅ are divalent aliphatic groups or aromatic groups, preferably an alkylene group,
Arylene group or those and -O- group, -CO- group, -S- group,
-SO- group, -SO ₂ -group, -NR ₉ -group (R ₉ is represented by the general formula (2), (3)
, And (synonymous with R _{7 of} (4)). More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or those and -S- group, -SO-
Is a divalent group formed by combining a group and a —SO ₂ — group, and R ₄ and R ₅ are arylene groups having 6 to 20 carbon atoms. Particularly, R ₅ is preferably a phenylene group. R ₃ , R ₄ and R ₅ may be substituted, and as the preferable substituents, those enumerated as the substituents for R ₁ are applicable.

In formulas (2) and (3), Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Preferable examples of the nitrogen-containing heteroaromatic ring formed by Z ₁ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, a pyrrole ring, an oxazole ring, a thiazole ring and benzo-condensation thereof. Other than the ring, a pteridine ring, a naphthyridine ring and the like can be mentioned. In formulas (2), (3) and (4), X ⁻ represents a counter anion or a counter anion moiety when forming an intramolecular salt. In the general formulas (3), (4) and (5), R ₆ represents an aliphatic group or an aromatic group. R ₆ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The three R _{6 s} in the general formula (4) may be the same or different, and may combine with each other to form a ring. Z ₁ and R ₆ may be substituted, and as the preferable substituents, those enumerated as the substituents for R ₁ are applicable. In the general formula (5), L ₃ is -CH ₂ CH.
₂ O- group, -CH ₂ CH (CH ₃ ) O- group, or -CH ₂ CH (OH) CH ₂ O- group, where n has the same meaning as in formula (1).

G ₁ in the general formula (1) is —CO— group,
The -SO ₂ -group is preferred, and the -CO- group is most preferred. A ₁ , A
₂ is preferably a hydrogen atom.

The alkyl group represented by R ₂ in the general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, a benzene ring). Including). G ₁
In the case of a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenyl Sulfonylmethyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(Eg, a hydroxymethylphenyl group), and a hydrogen atom is particularly preferable. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751.

R ₁ or R _{2 in} the general formula (1) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, Japanese Patent Application Laid-Open No. 1-10053
Those described in No. 0 are mentioned.

R ₁ or R _{2 in} the general formula (1) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, U.S. Pat. Nos. 4,385,108 and 4,459,347, and JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
47, 59-201, 048, 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned.

The compound of the general formula (1) of the present invention is disclosed in, for example, JP-A-61-213,847 and JP-A-62-260,153.
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-9.
8,803, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
No. 56-153,336, No. 56-153,34
No. 2, U.S. Pat. Nos. 4,988,604 and 4,994.
It can be synthesized by utilizing the method described in No. 365 or the like. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical formula 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

The addition amount of the compound of the general formula (1) of the present invention is 1 × 10 ⁻⁶ to 5 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-2 mol, and particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

The compound of the general formula (1) of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol,
It can be used by dissolving it in ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. In addition, by the well-known emulsion dispersion method, dibutyl phthalate,
Dissolved using an oil such as tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone,
It is also possible to mechanically prepare and use an emulsified dispersion. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The anionic surfactant suitable for use in the present invention is a surfactant containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group and a phosphoric acid ester group. HLB value of 8 to 14 (Here, the HLB value is based on the organic / inorganic method. For details, refer to Tsuji Recommended "Emulsification / Solubilization Technology" 3rd Edition (197).
9) Those having Kogyo Tosho Co., Ltd., pp. 10-11) are preferred. Typical examples of the anionic surfactant preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0035]

[Chemical 17]

However, R ¹⁰ is a saturated or unsaturated hydrocarbon having 3 to 20 carbon atoms and its fluorine substitution product, and R ¹¹ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. n is an integer of 1 to 20, particularly preferably 1 to 8. M is 1
It is a valent alkali metal, and Na and K are particularly preferable.

[0037]

[Chemical 18]

R ¹⁰ , M and n have the same meanings as in formula (6). a represents 0.1 or 2. m is an integer of 1 to 6, and 2 to 4 is particularly preferable.

[0039]

[Chemical 19]

R ¹⁰ and M have the same meanings as in formula (6).

[0041]

[Chemical 20]

However, R ¹¹ and M have the same meaning as in the general formula (6), and m has the same meaning as in the general formula (7).

[0043]

[Chemical 21]

R ¹⁴ is a saturated or unsaturated hydrocarbon in which a hydrogen moiety having 3 to 22 carbon atoms is fluorinated, and preferably has 7 to 18 carbon atoms. R ¹¹ and M have the same meaning as in formula (6), and m has the same meaning as in formula (7).
Specific examples of the anionic surfactants that are particularly preferably used are as follows.

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

The photosensitive silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide. The photosensitive silver halide used in the present invention is preferably fine particles having an average grain size (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodisperse means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size. The light-sensitive silver halide grains in a photographic emulsion may have a regular crystal such as a cube or octahedron, or may have an irregular crystal such as a sphere or a plate. It may be one having a compound form of these crystal forms. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof and the like are formed in the process of forming silver halide grains or physically ripening. May coexist. The emulsion layer of the present invention or other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive material in a bright room 350nm-600 to increase the
A dye having substantial light absorption in the nm region is used. These dyes are added to the emulsion layer depending on the purpose, or added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use. It depends on the molar extinction coefficient of the dye, but usually 10 ^-2 g
/ M ^{2 to 1} g / m ² is added. Preferably 50 mg
˜500 mg / m ² . Specific examples of dyes are disclosed in JP-A-63-6.
No. 4039 is described in detail, but some are shown below.

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

The above dye is dissolved in a suitable solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] to obtain the non-photosensitive hydrophilic property of the present invention. It is added to the coating solution for the colloid layer. These dyes are 2
It is possible to use a combination of two or more species. The dye of the present invention is
Used in the amount necessary to enable light room handling. The amount of the specific dye is generally ^{10 -3 g / m 2 ~1 g} / m 2, it is possible to find a preferable amount ranges particularly ^{10 -3 g / m 2 ~0.5g /} m 2.

The photosensitive silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination for chemical sensitization. Good. The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, iridium and other complex salts may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention. The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during production process of the light-sensitive material, storage during storage or photographic processing or stabilizing photographic performance. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine). Etc.), mucohalogen acids, etc. can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Hardening, and sensitization), various surfactants may be included. In particular, the surfactant preferably used in the present invention is JP-B-58-9.
It is a polyalkylene oxide having a molecular weight of 600 or more described in Japanese Patent No. 412. Also, a polymer latex such as polyalkyl acrylate may be incorporated for dimensional stability.

Suitable development accelerators or nucleating infectious development accelerators for use in the present invention are those disclosed in JP-A-53-77.
No. 616, No. 54-37772, No. 53-137, 1
No. 33, No. 60-140, No. 340, No. 60-1495.
In addition to the compounds disclosed in No. 9 and the like, various compounds containing an N or S atom are effective. Next, specific examples will be listed.

[0058]

[Chemical 28]

[0059]

[Chemical 29]

[0060]

[Chemical 30]

These accelerators depend on the kind of compound.
Optimal addition amount is different, but 1.0 × 10 ^-3~ 0.5 g / m²,
Preferably 5.0 × 10^-3~ 0.1 g / m²Used in the range of
Is desirable. Using the silver halide light-sensitive material of the present invention
In order to obtain ultra-high contrast photographic characteristics, conventional infectious developer and rice
To the pH 13 described in Japanese Patent No. 2,419,975
Stable development without the need to use a highly alkaline developer
A liquid can be used. That is, the halogen of the present invention
The silver halide photographic material contains 0.2% of sulfite ion as a preservative.
0 mol / liter or more, preferably 0.50 mol / liter
Including torr, pH 10.0-12.3, especially pH 10.5
With a developer of ~ 11.5, you can get a super-high contrast negative image.
Obtainable. Development that can be used in the method of the invention
There are no particular restrictions on the main drug, for example dihydroxybenze
(Eg, hydroquinone), 3-pyrazolidones
(For example, 1-phenyl-3-pyrazolidone, 4,4-di
Methyl-1-phenyl-3-pyrazolidone), aminophine
Enols (eg N-methyl-p-aminopheno
Can be used alone or in combination.
It The silver halide light-sensitive material of the present invention is particularly a main developing agent.
Dihydroxybenzenes as an auxiliary developing agent
Current compounds containing 3-pyrazolidones or aminophenols
Suitable to be treated with image liquid. Preferably this development
Dihydroxybenzenes in the liquid are 0.05 to 0.5
Mol / l, 3-pyrazolidones or aminofe
Nols should be used in combination within the range of 0.06 mol / liter or less.
Be done. As additives used in addition to the above components,
Acid, compounds such as borax, sodium bromide, potassium bromide
Development inhibitors such as aluminum and potassium iodide: ethylene glycol
, Diethylene glycol, triethylene glycol,
Dimethylformamide, methyl cellosolve, hexylene
Organic solvents such as glycol, ethanol, methanol:
1-phenyl-5-mercaptotetrazole, 5-nit
Indazole-based compounds such as leuindazole, 5-methyl
Benztriazole-based compounds such as benztriazole
Which antifoggant or black pepper inhibitor:
It may be contained, and if necessary, a toning agent, a surfactant,
A defoaming agent, a water softener, a hardener, etc. may be included. Starting
The developer used explicitly is JP-A-56-106244.
And the amine compounds described in Japanese Patent Application No. 1-291818
May be included. In the developer of the present invention, as a silver stain preventing agent
The compounds described in JP-A-56-24,347 are used.
You can As a dissolution aid to be added to a developing solution
The compounds described in 61-267759 can be used.
Wear. Further, as a pH buffering agent used in a developing solution, Japanese Patent Laid-Open No.
The compounds described in JP-A No. 0-93,433 or JP-A-62-62
The compounds described in 186259 can be used.
It Use a commonly used composition as the fixing agent.
You can As a fixing agent, thiosulfate and thiocyanate
In addition to phosphates, organics known to be effective as fixing agents
Sulfur compounds can be used. Hardener for fixer
Water soluble aluminum (eg aluminum sulfate, light
Van, etc.) may be included. Water soluble aluminum here
The amount of salt is usually 0.4 to 2.0 g-Al / liter
Is. Furthermore, trivalent iron compounds are used as oxidants in ethylene.
It can be used as a complex with diamine tetraacetic acid. Book
The treatment temperature in the process of the invention is usually between 18 ° C and 50 ° C.
Chosen in between. It is preferable to use an automatic processor for photo processing.
It is better to use the method of the present invention to process a photosensitive material in an automatic processor.
The total processing time from putting in to the coming out is 90
Even if it is set from 2 seconds to 120 seconds, it will be
Photographic properties are obtained.

[0062]

【Example】

Example 1 An emulsion was prepared as follows. Silver nitrate aqueous solution in a gelatin aqueous solution kept at 50 ° C and 4 x 10 per mol of silver
An aqueous solution of potassium iodide and potassium bromide containing ^-7 mol of K ₃ IrCl ₆ was added simultaneously for 60 minutes, during which pAg
Was maintained at 7.5 to prepare a monodisperse silver iodobromide emulsion (average grain size 0.28 μ, silver iodide amount 0.4 mol%). This emulsion was washed with water according to a conventional method to remove soluble salts, and potassium iodide was added to the emulsion to convert the grain surface, whereby the average silver iodide content of the grain / the silver iodide content of the grain surface = 1 / A silver iodobromide emulsion No. 3 was obtained.
Phenoxyethanol was added to this as a preservative.

3 × 10 ⁻⁴ mol of 5,5′-dichloro-9-ethyl-per 1 mol of silver was added to this emulsion as a sensitizing dye.
3,3'-Bis (3-sulfopropyl) oxacarbocyanine sodium salt was added, and 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-methylbenzotriazole, and the following compounds (a) and (b) were added so that each was coated at 5 mg / m ² .

[0064]

[Chemical 31]

Next, as shown in Table 1, an anionic surfactant was added so as to have a concentration of 0.1 mmol / m ² . Then, as shown in Table 1, the hydrazine compound was added as a methanol solution. The hydrazine compound for comparison is as follows.

[0066]

[Chemical 32]

Further, polyethylene glycol having an average molecular weight of 600 was added so as to have a concentration of 75 mg / m ^2, and the dispersion of polyethyl acrylate was 30 wt% of gelatin based on solid content.
%, 1,3-divinylsulfonyl-2-propanol was added as a hard film, and it was coated on a polyethylene terephthalate film so as to have a silver content of 3.5 g / m ² . (Gelatin 2g
/ M ² ) 1.2 g / m ² of gelatin as a protective layer, 40 mg / amorphous SiO ₂ matting agent having a particle size of about 3 μ
m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , hydroquinone 200 mg / m ² and silicone oil, the following compounds as preservatives

[0068]

[Chemical 33]

And phenoxyethanol and a fluorochemical surfactant represented by the following structural formula as a coating aid:

[0070]

[Chemical 34]

A layer containing sodium dodecylbenzene sulfonate was simultaneously applied to prepare a sample as shown in Table 1.

The back layer was applied by the following formulation. [Back layer formulation] Gelatin 4 g / m ² matting agent Polymethylmethacrylate (particle size 3.0 to 4.0 µ) 10 mg / m ² latex Polyethyl acrylate 2 g / m ² Surfactant p-dodecylbenzene sodium sulfonate 40 mg / m ²

Fluorine-based surfactant

[0074]

[Chemical 35]

Gelatin hardening agent

[0076]

[Chemical 36]

Dye Mixture of Dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0078]

[Chemical 37]

The coating solution for the back layer contains the following compounds as preservatives.

[0080]

[Chemical 38]

And phenoxyethanol were added.

When the above sample was applied, the application was performed under the following two conditions. Condition 1 A coating solution for the light-sensitive emulsion layer is added with additives, and then coating is carried out immediately (within 1 hour at the longest). Condition 2 A hardener and an additive other than polyethyl acrylate are added to the coating solution for the photosensitive emulsion layer, and the mixture is allowed to stand at 40 ° C. for 24 hours. Then, the hardener and polyethyl acrylate are added and coating is carried out immediately. Here, in order to evaluate the state of precipitation of the hydrazine compound in the coating liquid, the filtration time of the coating liquid was measured under the conditions of (Note 1) for each of Condition 1 and Condition 2. After exposing these samples with tungsten light through an optical wedge, Fuji Photo Film Co., Ltd. automatic processor FG
It was developed at -660 F with a developing solution having the following composition at 34 ° C. for 30 seconds, and fixing, washing with water and drying were sequentially performed.

[0083]

[Table 1]

[0084]

[Table 2]

Note 1: Filtration time of coating liquid: 100 ml of coating liquid
Is the time required for filtration with a microfilter having an average pore diameter of 10 μm and a diameter of 1.2 cm under a pressure of 1 pound / cm ² . Note 2: S in the photographic properties indicates the relative value (relative sensitivity) of the reciprocal of the exposure amount that gives a density of 3.0. Note 3: The filter was clogged and only part of 100 ml could be filtered.

From the results shown in Table 1, in Samples 1-2 and 1-3, when the coating solution was aged, precipitates were formed in the solution, the filter was clogged, and filtration was impossible.
It can be seen that the samples 1-5 and 1-6 of the present invention hardly cause clogging. Furthermore, samples 1-8 and 1 of the present invention
It can be seen that with -9, the hydrazine compound of the present invention specifically improves the filterability remarkably. Regarding the photographic properties, the hydrazine compound of the present invention (Samples 1-5 and 1-6) gives a sensitivity equal to or higher than that of the hydrazine compound of the comparative example (Sample 1-4). Further, Samples 1-5 and 1-6 of the present invention are Samples 1-2 and 1-3 in which no anionic surfactant is added.
It can be seen that the sensitivity is increased when there is no lapse of time (condition 1), and there is little change in performance even when there is lapse of time (condition 2). In addition, the effect is specifically increased by the hydrazine compound of the present invention in Samples 1-8 and 1-9. As described above, in the sample of the present invention, the hydrophobic hydrazine compound is stably dispersed, the reactivity of the hydrazine compound itself is not impaired, and on the contrary, the activity is increased. A high contrast image can be obtained. Further, the coating solution of the sample of the present invention is stable even after dissolution over time,
Excellent manufacturing stability.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising a hydrazine compound represented by the following general formula (1) and an anionic surfactant. [Chemical 1] In the formula, R ₁ represents an aliphatic group or an aromatic group, and -O- (CH ₂ CH ₂ O) _n- , -O- (CH ₂ CH
(CH ₃ ) O) _n -or -O- (CH ₂ CH (OH) CH ₂ O) _n- (however, n
Is a group containing a partial structure of 3 or more) or containing a quaternary ammonium cation as a part of the substituent. G ₁ is -CO- group, -COCO- group, -CS- group, -C (= NG ₂ R
₂₎ - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2) - represents a group. G ₂ is a simple bond, -O- group, -S- group or -N (R ₂ )
R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or arylsulfonyl group. 2. The anionic surfactant has the following general formula (6):
Alternatively, the silver halide photographic light-sensitive material according to claim 1, which is represented by (7). [Chemical 2] In the formula, R ¹⁰ is a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms and a fluorine-substituted product thereof, and R ¹¹ is a hydrogen atom, a methyl group, an ethyl group or a propyl group. n is an integer of 1 to 20, and M is a monovalent alkali metal. [Chemical 3] In the formula, R ¹⁰ , M and n have the same meanings as in formula (2). a represents 0, 1 or 2. m is an integer of 1 to 6.